High Pressure Preparation and Characterization of High Density ZrB2-ZrC Ultra-High Temperature Ceramic
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摘要: 超高温陶瓷具有高熔点、高热导率、抗氧化烧蚀等优异性能，是可重复使用的高超声速飞行器防热部件的重要候选材料之一。利用高压技术制备出了高致密超高温陶瓷ZrB2-ZrC复合材料。通过调控合成条件和原料配比，研究了合成压力和烧结助剂ZrC对复合材料抗热烧蚀性能的影响规律。结果表明：在压力3.2 GPa、温度950 ℃的条件下制备出的ZrB2-ZrC复合材料的致密度达到95%以上，该复合材料在1600 ℃烧蚀下的最优质量烧蚀率为17 μg/s，在2000 ℃下的最优质量烧蚀率为30 μg/s；在合成压力为2.9 GPa、温度为950 ℃的条件下，改变烧结助剂ZrC的含量可以影响复合材料的热烧蚀性能。其中，当ZrB2与ZrC的摩尔比为8∶1时，制备的ZrB2-ZrC复合材料经1600 ℃烧蚀后的质量烧蚀率达到最低值（35 μg/s）。Abstract: Ultra-high temperature ceramics have excellent properties, such as high melting point, high thermal conductivity, and anti-oxidative ablation, and thus are important candidates for reusable heat-resistant parts of hypersonic aircraft. In this paper, high-density and ultra-high temperature ceramic ZrB2-ZrC composites were prepared by high pressure technology. By adjusting the synthesis conditions and the ratio of raw materials, the effects of synthesis pressure and sintering aid ZrC content on the thermal ablation properties of the composites were studied. The results show that the density of ZrB2-ZrC composite prepared under 3.2 GPa and 950 ℃ is above 95%, and the optimal mass ablation rate of the composite at 1600 ℃ is 17 μg/s. The optimal mass ablation rate at 2000 ℃ is 30 μg/s. Under the synthesis pressure of 2.9 GPa and temperature of 950 ℃, by changing the content of the sintering aid ZrC, the thermal ablation performance of the composites could be affected. When the molar ratio of ZrB2 to ZrC is 8∶1, the mass ablation rate of the ZrB2-ZrC composites after ablation at 1600 ℃ has the lowest value (35 μg/s).
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图 1 不同压力下制备的ZrB2-ZrC复合材料样品的XRD谱
Figure 1. XRD patterns of the ZrB2-ZrC composites synthesized under different high pressures
图 2 不同压力下制备的ZrB2-ZrC复合材料样品表面的SEM图像
Figure 2. SEM images of the ZrB2-ZrC composites synthesized under different high pressures
图 3 温度950℃、不同压力下合成的ZrB2-ZrC复合材料经1600 ℃烧蚀后样品的XRD谱
Figure 3. XRD patterns of ZrB2-ZrC composite samples synthesized under different pressures at 950 ℃ after ablation at 1600 ℃
图 4 在2.6 GPa、950 ℃制备的ZrB2-ZrC复合材料经1600 ℃烧蚀后样品表面的SEM图像
Figure 4. SEM image of ZrB2-ZrC composite synthesized at 2.6 GPa and 950 ℃ after ablation at 1600 ℃
图 5 在3.2 GPa、950 ℃条件下制备的ZrB2-ZrC复合材料的原位高温XRD谱
Figure 5. In-situ high temperature XRD patterns of ZrB2-ZrC composite fabricated at 3.2 GPa and 950 °C
图 6 采用不同摩尔比的ZrB2和ZrC通过高压合成的复合材料样品的XRD谱
Figure 6. XRD patterns of composite samples synthesized with different molar ratios of ZrB2 and ZrC
图 8 1600 ℃烧蚀后ZrB2-ZrC复合材料样品截面的SEM图像
Figure 8. Cross-sectional SEM images of ZrB2-ZrC composites after ablation at 1600 ℃
图 9 ZrB2-ZrC复合材料样品（
$n_{{\rm{ZrB}}_2} $ ∶nZrC=8∶1）经1600 ℃烧蚀后的截面EDS图像Figure 9. EDS images of the cross-sectional sample of ZrB2-ZrC composite (
$n_{{\rm{ZrB}}_2} $ ∶nZrC=8∶1) after ablation at 1600 ℃表 1 不同压力下合成的ZrB2-ZrC复合材料样品经1600和2000 °C烧蚀后的烧蚀率
Table 1. Ablation rate of the ZrB2-ZrC composites synthesized at different pressures after ablations at 1600 and 2000 °C
Synthesis condition Ablation at 1600 ℃ Ablation at 2000 ℃ Rm/(μg·s−1) Rl/(μm·s−1) Rm/(μg·s−1) Rl/(μm·s−1) 2.6 GPa, 950 ℃ 67 0.17 230 4.16 2.9 GPa, 950 ℃ 55 0.15 260 4.60 3.2 GPa, 950 ℃ 17 0.16 30 6.00 
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表 2 高压制备的ZrB2-ZrC复合材料样品的致密度及其在1600 °C的烧蚀率
Table 2. Density and ablation rate at 1600 °C of ZrB2-ZrC composites prepared at high pressure
$n{_{{\rm{ZrB}}_2}} $∶nZrC Density/% Rm/(μg·s−1) Rl/(μm·s−1) 2∶1 95.4 55 0.15 4∶1 93.8 43 0.19 8∶1 95.4 35 0.19 16∶1 95.5 78 0.20
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